Method and structure for nonlinear optics

ABSTRACT

A nonlinear optical crystal having a chemical formula of Y i La j Al k B 16 O 48 , where 2.8≦i≦3.2, 0.8≦j≦1.2, i and j sum to about four, and k is about 12 is provided. The nonlinear optical crystal is useful for nonlinear optical applications including frequency conversion. Nonlinear optical crystals in a specific embodiment are characterized by UV blocking materials (e.g., some transition metals and lanthanides) at concentrations of less than 1,000 parts per million, providing high transmittance over portions of the UV spectrum (e.g., 175-360 nm).

CROSS-REFERENCES TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 13/040,215, filed Mar. 3, 2011; which is a division of U.S.patent application Ser. No. 12/404,289, filed Mar. 14, 2009, now U.S.Pat. No. 7,911,682 B2; which is a continuation of U.S. patentapplication Ser. No. 12/140,162, filed on Jun. 16, 2008, now U.S. Pat.No. 7,504,053 B1, issued on Mar. 17, 2009; which claims benefit under 35U.S.C. §119(e) of U.S. Provisional Patent Application No. 61/044,413,filed on Apr. 11, 2008. The disclosures of which are hereby incorporatedby reference in their entirety for all purposes.

BACKGROUND OF THE INVENTION

The present invention relates generally to certain compounds havingoptical properties. More particularly, as an example, an embodiment ofthe invention provides a specific compound comprisingR_(i)La_(j)Al_(k)B₁₆O₄₈, where 2.0≦i≦3.6, 0.4≦j≦2.0, i and j sum toabout four, k is about 12, and R is selected from an elemental groupconsisting of Y and Lu, for use with ultraviolet, visible, and infraredelectromagnetic radiation. More specifically, another embodimentprovides a compound comprising Y_(i)La_(j)Al_(k)B₁₆O₄₈, where 2.8≦i≦3.2,0.8≦j≦1.2, i and j sum to about four, and k is about 12, for use withultraviolet, visible, and infrared electromagnetic radiation. Merely byway of example, the compound is useful for electromagnetic radiationhaving wavelengths of 175-360 nm, but it would be recognized that theinvention has a much broader range of applicability.

Nonlinear optical (NLO) materials are unusual in that they affect theproperties of light. A well-known example is the polarization of lightby certain materials, such as when materials rotate the polarizationvectors of incident light. If the effect on the polarization vector bythe incident light is linear, then light emitted by the material has thesame frequency as the incident light. NLO materials affect thepolarization vector of the incident light in a nonlinear manner. As aresult, the frequency of the light emitted by a nonlinear opticalmaterial is affected, also described as frequency conversion/converters.

For example, when a beam of coherent light of a given frequency, such asproduced by a laser, propagates through a properly oriented NLO crystalhaving non-zero components of the second order polarizability tensor,the crystal will generate light at a different frequency, thus extendingthe useful frequency range of the laser. Generation of this light can beascribed to processes such as sum-frequency generation (SFG),difference-frequency generation (DFG) and optical parametricamplification (OPA). Devices using NLO crystals include, but are notlimited to up and down frequency converters, optical parametricoscillators, optical rectifiers, and optical switches.

Frequency generation in NLO materials is an important effect. Forexample, two monochromatic electromagnetic waves with frequencies ω₁ andω₂ propagating through a properly oriented NLO crystal can result ingeneration of light at a variety of frequencies. Mechanisms defining thefrequency of light using these two separate frequencies aresum-frequency generation (SFG) and difference-frequency generation(DFG). SFG is a process where light of frequency ω₃ is generated as thesum of the two incident frequencies, ω₃=ω₁+ω₂. In other words, SFG isuseful for converting long wavelength light to shorter wavelength light(e.g. near infrared to visible, or visible to ultraviolet). A specialcase of sum-frequency generation is second-harmonic generation (SHG)where ω₃=2ω₁, which is satisfied when the incident frequencies areequal, ω₁=ω₂. DFG is a process where light of frequency ω₄ is generatedas the difference of the incident frequencies ω₄=ω₁−ω₂. DFG is usefulfor converting shorter wavelength light to longer wavelength light (e.g.visible to infrared). A special case of DFG is when ω₁=ω₂, hence ω₄=0,which is known as optical rectification. Optical parametric oscillation(OPO) is also a form of DFG and is used to produce light at tunablefrequencies.

The conversion efficiency of an NLO crystal for a particular applicationis dependent on a number of factors that include, but are not limitedto: the effective nonlinearity of the crystal (pm/V), birefringence (Δn,where n is a refractive index), phase-matching conditions (Type I, TypeII, non-critical, quasi, or critical), angular acceptance angle(radian-cm), temperature acceptance (K-cm), walk-off (radian),temperature dependent change in refractive index (dn/dT), opticaltransparency range (nm), optical damage threshold (W/cm²), and opticallongevity. Desirable NLO crystals possess an optimal combination of theabove properties as defined by specific applications.

Optical materials commonly use boron as an elemental constituent becauseof its wide transparency and its robust bonding in oxides. Examplesinclude its use as glass-formers (borosilicate glasses), phosphors inthe form of powders, and as laser frequency converters. Borate crystalsare used in various applications, such as laser-based manufacturing,medicine, hardware and instrumentation, communications, and researchstudies. Several borate compounds are commonly used as crystals incommercial lasers: beta barium borate (BBO: β-BaB₂O₄), lithium triborate(LBO: LiB₃O₅), and cesium lithium borate (CLBO: CsLiB₄O₁₀). Thesecrystals are examples of borate-based NLO crystals developed in recentyears that are being used widely as NLO devices, especially inapplications that use ultraviolet light. Select properties suitable forgeneration of laser light from the mid-infrared to the ultraviolet forthese crystals are listed in Table 1.

TABLE 1 Commercially Available NLO Materials and Properties PROPERTY BBOLBO CLBO D_(eff) (pm/V) 2.2 0.8 0.9 Optical Transmission (nm) 190-3500160-2600 180-2750 Angular Acceptance (mrad-cm) 0.8 6.5 0.6 TemperatureAcceptance (K-cm) 55 7.5 2.5 Walk-off Angle (deg.) 3 0.6 1.8 DamageThreshold (GW/cm²) 5 10 10 Crystal Growth Properties flux or congr. fluxcongruent

BBO has a favorable nonlinearity (about 2.2 pm/V), transparency between190 nm and 3500 nm, significant birefringence (necessary for phasematching), and a good damage threshold (5 GW/cm², 1064 nm, 0.1 ns pulsewidth). However, its high birefringence creates a relatively smallangular acceptance that can limit conversion efficiencies and laser beamquality. The crystal is somewhat hygroscopic and is limited on theamount of optical power that can be transmuted.

LBO exhibits optical transparency throughout the visible electromagneticspectrum, extending well into the ultraviolet (absorption edge at about160 nm), and possesses a high damage threshold (10 GW/cm², 1064 nm, 0.1ns pulse width). However, it has insufficient intrinsic birefringencefor phase-matching to generate deep UV radiation.

CLBO appears capable of producing UV light due to a combination of highnonlinearity and sufficient birefringence. The crystal can also bemanufactured to relatively large dimensions. However, the crystal isexceedingly moisture sensitive and invariably absorbs water from theair; hence, extreme care usually must be taken to manage environmentalmoisture to prevent hydration stresses and possible crystal destruction.

Frequency conversion generally benefits from both high peak powers andtightly focused input beams, both of which increase the intensity of theinput and output beams within the nonlinear optical material. However,the lifetime of NLO materials under such conditions for UV productionlimits the usefulness of frequency-converted UV laser systems.Commercial DUV NLO devices of prior art are generally fabricated fromBBO and CLBO crystals. These NLO devices are unable to support longterm, high-output UV light because of their intrinsic weakness tomoisture. Water interacts with the material's surfaces and penetratesinto its bulk, causing breakdown in the presence of high intensity laserbeams. Previous attempts to mitigate this failure mode included usingenvironmental isolation with hermetic cells, elevated temperatures toreduce water sorption, purging dry gasses, and mechanical devices toshift the position of the crystal relative to the laser beam.Ultimately, it is very difficult to overcome the intrinsic materialfailings of BBO and CLBO for deep UV NLO processes.

A related consequence to the hygroscopic nature of BBO and CLBO is thatthese NLO materials are limited in the degree to which they are able tosupport high intensity radiation. With activation energy supplied byhigh intensity input beams, surface damage on the polished faces isquickly promoted in the presence of water. The degradation propagatesalong the beam path into the bulk device, driven by the high intensitylaser beam. This phenomenon limits the amount and duration of inputlaser radiation through the frequency converter. As a result, conversionefficiencies remain well below optimum and device operational lifetimesare significantly compromised. Clearly, a new UV frequency converterthat is impervious to water represents the real solution to the problem.

To address these concerns for conventional UV NLO crystals, several morerecent materials have been considered but have not yet realizedcommercial relevance: compounds such as potassium aluminum borate(K₂Al₂B₂O₇), yttrium lanthanum scandium borate ((Y,La)Sc₃(BO₃)₄), andstrontium beryllium borate (Sr₂Be₂B₂O₇). These materials have appearedin research discussions and offered improved resistance against moistureintrusion, but issues such as crystal growth constraints, inadequate orunsuitable optical properties, difficulty of manufacture, laser damage,etc. have prevented these and other candidates from becoming practicalcrystals for frequency conversion.

Another material considered as a UV-grade NLO frequency converter isYAl₃(BO₃)₄. This base formulation was put forward in 1960 by Ballman,and his potassium molybdate solvent of making crystals therein hasremained as the primary means of growing crystal. As such and throughthe years, the pure form of YAB has not been commercially produced. Theconventional method of production yields small crystal that contains alarge amount of nonstoichiometric metals contamination and exhibitssubstandard crystal quality. Moreover, the solvent used introduces aconsiderable amount of contaminant that prevents device operation in theultraviolet. The summary of work on huntite borates by Leonyuk & Leonyuk(1995) described a flux system that has subsequently remained as amethod of producing YAB and its family members, namely the potassiummolybdates K₂MoO₄ and K₂Mo₃O₁₀. Unfortunately, these solventformulations possess severe limitations for large scale crystal growth:a) high flux volatility, b) small crystal yield, and c) significantinclusion of Mo atoms into the crystalline structure. This latter issuerevealed the lower spectral limit of optical use, described as 350-360nm.

Again, its operation and the historic method of preparation limit itsuse to the visible and infrared. Hence, it is highly desirable toimprove techniques for this family of compounds that enable opticalfunction down into the ultraviolet. Thus, there is a need in the art forimproved methods and techniques for optical compounds.

SUMMARY OF THE INVENTION

According to the present invention, techniques related generally tocertain compounds having optical properties are provided. Moreparticularly, as an example, an embodiment of the invention provides aspecific compound comprising R_(i)La_(j)Al_(k)B₁₆O₄₈, where 2.0≦i≦3.6,0.4≦j≦2.0, i and j sum to about four, k is about 12, and R is selectedfrom an elemental group consisting of Y and Lu, for use withultraviolet, visible, and infrared electromagnetic radiation. Morespecifically, another embodiment provides a compound comprisingY_(i)La_(j)Al_(k)B₁₆O₄₈, where 2.8≦i≦3.2, 0.8≦j≦1.2, i and j sum toabout four, and k is about 12, for use with ultraviolet, visible, andinfrared electromagnetic radiation. Merely by way of example, thecompound is useful for electromagnetic radiation having wavelengths of175-360 nm, but it would be recognized that the invention has a muchbroader range of applicability.

According to one embodiment of the present invention, a compound fornonlinear optics is provided. The compound includes a material fornonlinear optics comprising R_(i)La_(j)Al_(k)B₁₆O₄₈, where R═Y, i isabout 3.04, j is about 0.96, and k is about 12. The elementalproportions of this compound is representative of a unique andstabilized phase that can preferentially emerge from the invention'srange of composition 2.0≦i≦3.6 and 0.4≦j≦2.0. By way of example,R₃LaAl₁₂B₁₆O₄₈ (0.25 mol) represents a unique composition where R═Yand/or Lu, i is 3.00, and j is 1.00.

According to another embodiment of the present invention, a compound fornonlinear optics is provided. The compound includes a material fornonlinear optics comprising Y_(i)La_(j)Al_(k)B₁₆O₄₈, where i is about3.04, j is about 0.96, and k is about 12. The elemental proportions ofthis compound are representative of a unique and stabilized phase thatcan preferentially emerge from the invention's range of composition2.8≦i≦3.2 and 0.8≦j≦1.2. By way of example, Y₃LaAl₁₂B₁₆O₄₈ represents aunique composition where i is 3, j is 1, and k is 12.

According to a specific embodiment, a composition of matter having thegeneral formula R_(i)La_(j)Al_(k)B₁₆O₄₈ is provided, where 2.0≦i≦3.6,0.4≦j≦2.0, i and j sum to about four, k is about 12, and R is selectedfrom an elemental group consisting of Y and Lu.

According to yet another embodiment of the present invention, a compoundfor nonlinear optics for use at wavelengths of 175-360 nm comprising amaterial for nonlinear optics includes R_(i)La_(j)Al_(k)B₁₆O₄₈, where2.0≦i≦3.6, 0.4≦j≦2.0, i and j sum to about four, k is about 12, and R isselected from an elemental group consisting of Y and Lu, for use withpreferred wavelengths of electromagnetic radiation.

According to yet another embodiment of the present invention, a methodfor making a compound for nonlinear optics for use at wavelengths of175-360 nm includes providing a plurality of materials. The plurality ofmaterials includes an yttrium bearing compound and the yttrium bearingcompound is capable of being decomposed into at least yttrium oxide uponheating. Additionally, the method includes mixing the plurality ofmaterials to form a mixture based on at least information associatedwith a predetermined proportion, starting a crystallization process inthe mixture to form a crystal, and removing the crystal from themixture, the crystal including yttrium.

According to yet another embodiment of the present invention, a methodfor making a compound for nonlinear optics for use at wavelengths of175-360 nm includes providing a plurality of materials. The plurality ofmaterials includes a lutetium bearing compound, and the lutetium bearingcompound is capable of being decomposed into at least lutetium oxideupon heating. Additionally, the method includes mixing the plurality ofmaterials to form a mixture based on at least information associatedwith a predetermined proportion, starting a crystallization process inthe mixture to form a crystal, and removing the crystal from themixture, the crystal including lutetium.

According to yet another embodiment of the present invention, a methodfor making a compound for nonlinear optics for use at wavelengths of175-360 nm includes providing a plurality of materials. The plurality ofmaterials includes a lanthanum bearing compound, and the lanthanumbearing compound is capable of being decomposed into at least lanthanumoxide upon heating. Additionally, the method includes mixing theplurality of materials to form a mixture based on at least informationassociated with a predetermined proportion, starting a crystallizationprocess in the mixture to form a crystal, and removing the crystal fromthe mixture, the crystal including lanthanum.

According to yet another embodiment of the present invention, a methodfor making a compound for nonlinear optics for use at wavelengths of175-360 nm includes providing a plurality of materials. The plurality ofmaterials includes an aluminum bearing compound, and the aluminumbearing compound is capable of being decomposed into at least aluminumoxide upon heating. Additionally, the method includes mixing theplurality of materials to form a mixture based on at least informationassociated with a predetermined proportion, starting a crystallizationprocess in the mixture to form a crystal, and removing the crystal fromthe mixture, the crystal including aluminum.

According to yet another embodiment of the present invention, a methodfor making a compound for nonlinear optics for use at wavelengths of175-360 nm includes providing a plurality of materials. The plurality ofmaterials includes a boron bearing compound, and the boron bearingcompound is capable of being decomposed into at least boron oxide uponheating. Additionally, the method includes mixing the plurality ofmaterials to form a mixture based on at least information associatedwith a predetermined proportion, starting a crystallization process inthe mixture to form a crystal, and removing the crystal from themixture, the crystal including boron.

In a specific embodiment, a composition of matter (also referred to as acompound) having the general formula comprising R_(i)La_(j)Al_(k)B₁₆O₄₈is provided. In this specific embodiment, 2.0≦i≦3.6, 0.4≦j≦2.0, i and jsum to about four, k is about 12, and R is selected from an elementalgroup consisting of Y and Lu. In some nonlinear optical applications,the composition of matter is useful at wavelengths of less than or equalto about 360 nm. The compound may be a crystal phase. Additionally, thecompound may include one or more bearing UV-blocking impurities at aconcentration of less than 1000 parts per million. The one or moreUV-blocking impurities may include a transition metal element or alanthanide element other than Y, La, or Lu.

In a particular embodiment, the compound is free from bearingUV-blocking impurities of at least 1000 parts per million. Some uses ofthe compound as a nonlinear optical element are in the wavelength rangefrom about 360 nm to about 175 nm. Other uses of the compound as anonlinear optical element are in device (e.g., an NLO system, a lightsource, or a laser system) generating optical radiation at a wavelengthless than 360 nm. In one embodiment, the compound is associated with thetrigonal crystal class of space group R32 for use below 360 nm. Thecompound may have a volume greater than about 0.01 mm³, about 0.1 mm³ orabout 1 mm³.

In another specific embodiment, a method of growing single crystals of acomposition is provided, having the general formulaR_(i)La_(j)Al_(k)B₁₆O₄₈, where 2.0≦i≦3.6, 0.4≦j≦2.0, i and j sum toabout four, k is about 12, and R is selected from an elemental groupconsisting of Y and Lu is provided. The method includes heating theconstituent components of the composition to a temperature on the orderof 1500 K with a mixture of lanthanum oxide and boron oxide, the moleratio of lanthanum compound to boron compound being in the range of 1:4to 1:6, the nutrient-to-solvent ratio being in the range of 2:3 to 1:3,and cooling the resultant melt, whereby the composition precipitatesfrom the melt as one or more crystals. In the method, cooling theresultant melt may be performed at a temperature rate of less than 1 Kper day.

According to yet another specific embodiment, a method for making acompound for nonlinear optics for use at 360 nm and below is provided.The method includes providing a plurality of materials (e.g., lanthanumoxide or boron oxide). The plurality of materials includes a lanthanumbearing compound, the lanthanum bearing compound being capable of beingdecomposed into at least lanthanum oxide upon heating. The method alsoincludes mixing the plurality of materials to form a mixture based on atleast information associated with a predetermined proportion, starting acrystallization process in the mixture to form a huntite crystal (e.g.,by inserting a crystalline seed to a melt surface), and removing thehuntite crystal from the mixture. The huntite crystal includeslanthanum. In a exemplary, the crystal includes R_(i)La_(j)Al_(k)B₁₆O₄₈,where 2.0≦i≦3.6, 0.4≦j≦2.0, i and j sum to about four, k is about 12,and R is selected from an elemental group consisting of Y and Lu.

The method may utilize a plurality of materials including a ratio ofY:La ranging from 4:6 to 4:16. The method may further include placingthe mixture into a furnace or heating the mixture to a firstpredetermined temperature and cooling the mixture to a secondpredetermined temperature.

According to an additional embodiment, a method for making a compoundfor nonlinear optics for use at 360 nm and below is provided. The methodincludes providing a plurality of materials (e.g., yttrium oxide orboron oxide). The plurality of materials includes an yttrium bearingcompound being capable of being decomposed into at least yttrium oxideupon heating. The method also includes mixing the plurality of materialsto form a mixture based on at least information associated with apredetermined proportion, starting a crystallization process in themixture to form a crystal (by inserting a crystalline seed to a meltsurface), and removing the crystal from the mixture. The crystalincludes yttrium. The crystal may be a composition of matter having thegeneral formula R_(i)La_(j)Al_(k)B₁₆O₄₈, where 2.0≦i≦3.6, 0.4≦j≦2.0, iand j sum to about four, k is about 12, and R is selected from anelemental group consisting of Y and Lu.

The method may also include placing the mixture into a furnace orheating the mixture to a first predetermined temperature and cooling themixture to a second predetermined temperature.

Many benefits are achieved by way of the present invention overconventional techniques. For example, some embodiments of the presentinvention provide new methods of preparation that exclude contaminantsthat preclude the optical operation of borate huntites in theultraviolet spectrum. In addition, a preparative method has beendeveloped to allow rapid formation of crystal by using an inventivechemical recipe. Such methods enable the manufacture of large singlecrystals of the present invention, heretofore unattained in conventionalmethods. Also, a preparative method has been developed with a lowervolatility of the starting mixture when heated to a melting temperaturethan conventional methods.

Various additional objects, features and advantages of the presentinvention can be more fully appreciated with reference to the detaileddescription and the accompanying drawings that follow.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a simplified flowchart illustrating a method of making anoptical compound according to an embodiment of the present invention;

FIG. 2 is a simplified image of an optical compound according to anembodiment of the present invention;

FIG. 3 is a simplified diagram showing transmission characteristics foran optical compound according to an embodiment of the present invention;

FIG. 4A is a simplified diagram showing frequency conversion by anoptical compound according to an embodiment of the present invention;

FIG. 4B is a spectral profile for the converted 266 nm light; and

FIG. 5 shows typical long term behavior of 266 nm generated radiationfrom UV-grade huntite, BBO, and CLBO crystalline devices.

DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS

According to the present invention, techniques related generally tocertain compounds having optical properties are provided. Moreparticularly, as an example, an embodiment of the invention provides aspecific compound comprising R_(i)La_(j)Al_(k)B₁₆O₄₈, where 2.0≦i≦3.6,0.4≦j≦2.0, i and j sum to about four, k is about 12, and R is selectedfrom an elemental group consisting of Y and Lu, for use withultraviolet, visible, and infrared electromagnetic radiation. Morespecifically, another embodiment provides a compound comprisingY_(i)La_(j)Al_(k)B₁₆O₄₈, where 2.8≦i≦3.2, 0.8≦j≦1.2, i and j sum toabout four, and k is about 12, for use with ultraviolet, visible, andinfrared electromagnetic radiation. Merely by way of example, thecompound is useful for electromagnetic radiation having wavelengths of175-360 nm, but it would be recognized that the invention has a muchbroader range of applicability.

According to certain embodiments of the present invention, several kindsof borate crystals containing one or more kinds of Group 3, Group 13,and 4f metals and the like were prepared, and an occurrence experimentof an ultraviolet harmonic (wavelength: 266 nm) was carried out byirradiating with a green light laser (wavelength: 532 nm) onto theseborate crystals. Thereby, the ability to experimentally make NLOmaterials was demonstrated that produce harmonic light below 360 nm. Asa result, strong generation of second harmonic 266 nm from boratecrystals was found that includes Y, La, and Al, and a novel NLO crystalin the form of yttrium lanthanum aluminum borate was achieved capable oftransmitting and producing ultraviolet radiation below 360 nm.

Because of its intrinsic non-hygroscopic nature, compounds describedherein allow for relaxation of the need for crystal protection. Inaddition to supporting shorter-than-typical crystal lengths, thepreferred materials provided by embodiments of the present inventionallow a significant simplification in the mechanical design of the laserapparatus, namely the omission of an environmental isolation chambersurrounding the material or reductions in typical requirements. Purgedor sealed environmental chambers are typically necessary in UV lasersthat employ CLBO or BBO primarily due to their hygroscopicity. Incontrast, the preferred materials (also referred to as the principalcompound) remain insensitive to the presence of water, and therefore,water-based optical degradation has not been shown to be evident. Assuch, the non-hygroscopic nature of the principal compound directlyimparts operational longevity as a constituent of a laser apparatus. Theprincipal compounds provided by embodiments of the present inventiondemonstrate the lack of moisture uptake, and under ambient conditions,no long-term optical degradation is observed. By way of comparison,prior art materials BBO and CLBO are notorious for break down over timeas a result of their reactivity with water vapor. FIG. 5 shows typicallong term behavior of 266 nm generated radiation from UV-gradeY_(i)La_(j)Al_(k)B₁₆O₄₈ in the mole fractions described herein, BBO, andCLBO crystalline devices. Mere ambient atmospheric moisture issufficient to cause degradation of the commercial UV NLO materials in amatter of minutes of operation. This situation is of grave consequencefor the use of BBO and CLBO frequency conversion devices in lasers,where the laser apparatus suffers diminished operational longevity andrequires momentous design complexity/compromise to manage frequencyconverter crystal issues. The lack of the need for environmentalisolation results in a very significant reduction in the complexity,cost, and required maintenance of the frequency converted laserapparatus and represents an overall improvement to the design andoperation of the laser apparatus.

Embodiments of the present invention benefit from another feature of theNLO devices made from the principal compound, sans UV-inhibitingcontaminants: the functional improvement of optical transmission in theUV. Contaminants that contribute to transmission loss cause localizedheat generation and thermal de-phasing in the NLO device. While theprimary effort by some embodiments of the invention is directed towardthe reduction of spectrally-absorptive moieties (e.g. transition metalatoms) within NLO devices, de-phasing may be managed to some degree bythermally controlling the NLO device. Direct bonding of the NLO deviceto metal is an efficient means of regulating crystal temperature. Thenon-hygroscopic nature of the crystals included within the scope of thepresent invention permits the ability for it to be directly bonded tometal with solder and flux, thereby allowing the bonded crystal to bewashed in aqueous-based or non-aqueous solvents.

It is an object of certain embodiments of the present invention toproduce and utilize nonlinear optical materials that satisfyR_(i)La_(j)Al_(k)B₁₆O₄₈, where 2.0≦i≦3.6, 0.4≦j≦2.0, i and j sum toabout four, k is about 12, and R is selected from an elemental groupconsisting of Y and Lu, and manufactured by a method that eliminates orsignificantly reduces contaminants that prohibit device use in the UVspectrum. It is an object of other embodiments to provide an opticalmaterial or principal compound having the chemical formulaY_(i)La_(j)Al_(k)B₁₆O₄₈, where 2.8≦i≦3.2, 0.8≦j≦1.2, i and j sum toabout four, and k is about 12. In a particular embodiment, the opticalmaterial is characterized by an absence of reduction in the presence ofcontaminants that reduce the transmission of the optical material in theUV range (e.g., below 360 nm). More specifically, some embodiments ofthe present invention substantially exclude metals, such as those ofd-block transition metals, and/or most 4f-block metals (e.g.,lanthanides), from being present in the device so as to be useful in theUV below 360 nm.

It is an object of some embodiments of the present invention to providemethods for making nonlinear optical materials that satisfy the abovecomposition without deleterious UV absorption. One embodiment comprisesforming a mixture comprising from about 5 to about 20 wt % of a sourceof R, from about 20 to about 50 wt % of La, from about 7 to about 25 wt% of a source of Al, and from about 30 to about 50 wt % of boron oxide.If R is Y, then the source of R is generally yttrium oxide; if R is Lu,then the source of R is generally lutetium oxide. The source of La isgenerally lanthanum oxide, the source of Al is generally aluminum oxide,and the source of B is generally boron oxide or boric acid. The mixtureis heated to a temperature and for a period of time sufficient to formthe NLO material. For instance, the step of heating may comprise heatingthe mixture to a first temperature of at least 100 K, and generallygreater than about 1000 K. The mixture is then cooled. After cooling themixture is comminuted (ground to a fine powder, such as by grinding witha mortar and pestle), and then heated to a second temperature of atleast 1300 K, generally greater than about 1300 K.

Another method to form these crystalline materials may be but notlimited to top-seeded solution growth as shown in FIG. 1. The methodincludes the following processes:

-   -   1. High purity oxide powders and chemicals are measured and        mixed in appropriate proportions.    -   2. The mixture is loaded in a crucible and placed in a furnace.    -   3. The mixture is heated and caused to melt into a liquid.    -   4. After a time, melt temperature is brought near to its        freezing point.    -   5. A cold finger material or a seed crystal is introduced to        initiate crystallization.    -   6. Melt temperature and apparatus conditions are modified and        monitored to encourage crystal growth.    -   7. When appropriate, the system is brought down to room        temperature.    -   8. The crystal is removed from the system.

It should be appreciated that the specific steps illustrated aboveprovide a particular method of synthesizing a nonlinear crystalaccording to an embodiment of the present invention. Other sequences ofsteps may also be performed according to alternative embodiments. Forexample, alternative embodiments of the present invention may performthe steps outlined above in a different order. Moreover, the individualsteps illustrated above may include multiple sub-steps that may beperformed in various sequences as appropriate to the individual step.Furthermore, additional steps may be added or removed depending on theparticular applications. One of ordinary skill in the art wouldrecognize many variations, modifications, and alternatives.

For example, the synthesis of Y₃LaAl₁₂B₁₆O₄₈ may be performed asfollows. Yttrium oxide (Y₂O₃), having a purity of greater than 99.9%,lanthanum oxide (La₂O₃), having a purity of greater than 99.9%, aluminumoxide (Al₂O₃), having a purity greater than 99.9%, and boron oxide(B₂O₃), having a purity of greater than 99.9% were purchased fromcommercial vendors such as Aesar and Stanford Materials. A mixture wasformed including about 13 wt % yttrium oxide, about 30 wt % lanthanumoxide, about 17 wt % aluminum oxide, and about 40 wt % boron oxide. Thisrepresents Step 1 of the above procedure. Steps 2-8 are conducted toform a crystal of the principal compound formulation with some remainingstoichiometric material residing in the crucible that serves as fluxingagents.

As discussed above, certain embodiments of the present invention arerelated to nonlinear optical (NLO) devices and electrooptic devices andthe ability to employ such devices below 360 nm. Some embodiments of thepresent invention are related to nonlinear optical materials thatsatisfy the general formula R_(i)La_(j)Al_(k)B₁₆O₄₈, where 2.0≦i≦3.6,0.4≦j≦2.0, i and j sum to about four, k is about 12, and R is selectedfrom an elemental group consisting of Y and Lu and are prepared withoutcontaminants that prevent use in the ultraviolet (UV) section of theelectromagnetic spectrum. Other embodiments are related to nonlinearoptical materials that satisfy the general formulaY_(i)La_(j)Al_(k)B₁₆O₄₈, where 2.8≦i≦3.2, 0.8≦j≦1.2, i and j sum toabout four, and k is about 12. These materials may be prepared so thatthe presence of contaminants that prevent use in the ultraviolet (UV)section of the electromagnetic spectrum are limited to predeterminedlevels.

UV-inhibiting contaminants can be introduced by several sourcesthroughout the process of making crystals. The most significant sourceof contaminants is the starting materials. By utilizing very high puritychemical ingredients, embodiments reduce UV absorbing 3d-5d transitionmetals (e.g., elements 22-32, 40-52, and 72-84) and most lanthanides(e.g., elements 58-70) to concentration levels typically less than 10ppm. In some embodiments, the concentrations of these elements is atlevels less than 1000 ppm. Other concentrations are described throughoutthe present specification.

The other major contamination component is the charge crucible.Preferably, the charge crucible is inert with respect to the nutrient,tolerant of the top furnace temperature, and mechanically strong overthe process temperature range. The charge crucible is typically madeusing platinum group metals, with Pt surfaces being the most preferredbecause of their inert nature with respect to oxides and oxygen. Otherconsiderations in reducing the presence of UV absorbing contaminantsinclude the use of high purity furnace ceramics of sufficient thermalintegrity, controlled atmospheric gas purity, and inert means ofsecuring the crystallization seed. With control of contaminants in thestarting materials and the furnace, UV-blocking contaminants are held toa level that does not compromise the primary material's intrinsic UVtransmission properties.

According to some embodiments of the present invention, the nonlinearoptical material is used as an NLO device for operation below 360 nm. Inanother example, the nonlinear optical material is used with a lasersource for a device that generates optical radiation below 360 nm. Inyet another example, the nonlinear optical material is used with a lightsource for a device that generates optical radiation below 360 nm. Inyet another example, the nonlinear optical material is formed in thetrigonal crystal class for use below 360 nm. In yet another example, thenonlinear optical material is formed in the space group R32 for usebelow 360 nm.

It is an object of certain embodiments of the present invention toproduce and utilize nonlinear optical materials that satisfyY_(i)La_(j)Al_(k)B₁₆O₄₈, where 2.8≦i≦3.2, 0.8≦j≦1.2, i and j sum toabout four, and k is about 12 and manufactured by a method thateliminates or significantly reduces contaminants that prohibit deviceuse in the UV spectrum. More specifically, some embodiments of thepresent invention substantially exclude transition metals from beingpresent in the device so as to be useful in the UV below 360 nm. In aspecific embodiment, the UV transmission of select borate huntites isextended by avoiding the inclusion of 3d-5d transition metals (e.g.,elements 22-30, 40-48, and 72-80) and non-stoichiometric lanthanideimpurities (e.g., elements 58-70). For example, the inclusion of suchelements may be at a level of less than 10,000, 5,000, 2,000, 1,000,500, 250, 100, 50, or 10 parts per million. In addition, the absence ofsuperfluous metals in the primary crystal composition reduces theoverall bulk spectral absorption over its entire transparency range,such as from 175 to 2500 nm. With the embodiments described herein, theintrinsic transparency may be realized. Thus, in some embodiments, theoptical transmittance of the composition of matter is greater than 0.9at 250 nm. This particular value and wavelength is not intended to limitembodiments of the present invention, but to serve as an example of theoptical properties of the crystals described herein. In otherembodiments, the optical transmittance is greater than 0.7, greater than0.75, greater than 0.8, greater than 0.85, or greater than 0.9 at 200nm. In yet other embodiments, the optical transmittance is greater than0.8, greater than 0.85, greater than 0.9, or greater than 0.95 at 250nm, or the like. One of ordinary skill in the art would recognize manyvariations, modifications, and alternatives.

As discussed above, it is an object of some embodiments of the presentinvention to provide methods for making nonlinear optical materials thatsatisfy R_(i)La_(j)Al_(k)B₄O₁₂, where 0.5≦i≦0.9, 0.1≦j≦0.5, i and j sumto about one, k is about three, and R is selected from an elementalgroup consisting of Y and Lu, without the deleterious UV absorption. Insome embodiments, the NLO materials satisfy Y_(i)La_(j)Al_(k)B₁₆O₄₈,where 2.8≦i≦3.2, 0.8≦j≦1.2, i and j sum to about four, and k is about12. One embodiment comprises forming a mixture comprising from about 10to about 30 mol % of a source of R (e.g., Y), from about 10 to about 40mol % of La (e.g., lanthanum oxide), from about 10 to about 25 mol % ofa source of Al (e.g., aluminum oxide), and from about 25 to about 50 mol% of boron oxide. If R is Y, then the source of Y generally is yttriumoxide; if R is Lu, then the source of Lu is generally is lutetium oxide.The mixture is heated to a temperature and for a period of timesufficient to form the NLO material. For instance, the step of heatingmay comprise heating the mixture to a first temperature of at least 1000K, and generally greater than about 1000 K. The mixture is then cooled.After cooling the mixture is comminuted (ground to a fine powder, suchas by grinding with a mortar and pestle), and then heated to a secondtemperature of at least 1300 K, generally greater than about 1300 K.

As discussed above, FIG. 1 is a simplified method for making opticalcompound according to an embodiment of the present invention. Thisdiagram is merely an example, which should not unduly limit the scope ofthe claims. One of ordinary skill in the art would recognize manyvariations, alternatives, and modifications. The method 100 includes aprocess 110 for measuring and mixing chemicals (e.g., a set ofconstituent components), a process 120 for transferring mixture tocrucible and furnace, a process 130 for melting mixture, a process 140optimizing furnace conditions for crystallization, a process 150 forintroducing seed and starting crystallization, and a process 160 forcooling system and extracting crystal. Although the above has been shownusing a selected sequence of processes, there can be many alternatives,modifications, and variations. For example, some of the processes may beexpanded and/or combined. Other processes may be inserted to those notedabove. Depending upon the embodiment, the specific sequence of processesmay be interchanged with others replaced. For example, the process 150is modified to use spontaneous nucleation, or use conventional opticalcrystal growth procedures to introduce a cold finger to the meltsurface. Further details of these processes are found throughout thepresent specification and more particularly below.

At the process 110, certain chemicals (i.e., a set of constituentcomponents) are measured and mixed. For example, high purity oxidepowders and chemicals are measured and mixed in appropriate proportions.At the process 120, the mixture is transferred to crucible and furnace.For example, the mixture is loaded in a crucible and placed in afurnace. At the process 130, the mixture is melted. For example, themixture is heated and caused to melt into a liquid.

At the process 140, furnace conditions are optimized forcrystallization. For example, after a time, the melt temperature isbrought near to its freezing point. At the process 150, a seed isintroduced and the crystallization is started. For example, a seedcrystal is introduced to initiate crystallization. In another example,the process 150 is modified to use a cold finger material to initiatecrystallization. In yet another example, the process 150 is modified touse spontaneous nucleation to initiate crystallization. Additionally,the melt temperature and apparatus conditions are modified and monitoredto encourage crystal growth. At the process 160, the system is cooledand the crystal is extracted. For example, when appropriate, the systemis brought down to room temperature. The crystal is removed from thesystem and ready for tests or further processing.

As an example for the method 100, the synthesis of R₃LaAl₁₂B₁₆O₄₈, whereR=Y is performed as follows:

At the process 110, yttrium oxide (Y₂O₃), having a purity of greaterthan 99.9%, lanthanum oxide (La₂O₃), having a purity of greater than99.9%, aluminum oxide (Al₂O₃), having a purity greater than 99.9%, andboron oxide (B₂O₃), having a purity of greater than 99.9% are obtained.For example, these chemicals are acquired from commercial vendors suchas Aesar and Stanford Materials. A mixture is formed including about 12wt % Y₂O₃, about 33 wt % La₂O₃, about 16 wt % Al₂O₃, and about 39 wt %B₂O₃ as the set of constituent components. In a particular embodiment,the yttrium source and the aluminum source are provided and then aremixed with a lanthanum source and a boron source. The set of constituentcomponents may be characterized by a predetermined amount of nutrientsand a predetermined amount of solvents. In an embodiment, the mole ratioof lanthanum to yttrium is in a range of more than 1.5:1 and a moleratio of the predetermined amount of nutrients to the predeterminedamount of solvents is in a range of 1:1 to 1:5. Other ranges suitablefor forming compositions of matter in accordance with embodiments of thepresent invention are also included within the scope of the presentinvention.

At the process 120, the mixture is loaded into a crucible and placed ina high-temperature furnace with atmospheric environment control. Forexample, either ambient or an inert atmosphere is satisfactory. At theprocess 130, the mixture is heated in 12 hours from room temperature toa predetermined temperature ranging from 1450 to 1575 to thereby form aresultant melt. In a preferred embodiment, the predetermined temperatureis approximately 1500 K, for example, between 1450 and 1575 K, between1475 and 1550 K, or between 1475 and 1525 K. The resulting melt isallowed to soak at the predetermined or another temperature for apredetermined period of time (e.g., about 1 to 3 days).

At the process 140, the liquid mixture (i.e., the resultant melt) iscooled at a rate of less than or equal to 20 K/hour to a temperaturenear its freezing point. For example, the temperature ranges from about1500 to 1400 K. At the temperature, the mixture is held for about 8hours. In other embodiments, the mixture is held at the temperature forother times, for example, a time ranging from about 8 hours to about 72hours. In a particular embodiment, the time is 48 hours. At the process150, by spontaneous nucleation, or by using conventional optical crystalgrowth procedures to introduce a crystalline seed or cold finger to themelt surface, the product begins to form while cooling to a finaltemperature of 1300 K at a rate of about 1-5 K/day. Thus, in embodimentsof the present invention, one or more nonlinear crystals are formed as aprecipitate from the resultant melt. Additionally, during the course ofthe growth, the melt temperature and apparatus conditions are monitoredand optionally modified to encourage crystal growth, either by anoperator and/or by the automated control system on the furnace.

At the process 160, the system is then cooled to room temperature at acooling rate of about 50 K/hour. One or more colorless, transparentcrystals of Y₃LaAl₁₂B₁₆O₄₈ are obtained and removed from the furnace.Although in the embodiment described above, the crystal formula isY₃LaAl₁₂B₁₆O₄₈, other chemical formulas are included within the scope ofthe present invention, including yttrium mole fractions ranging fromabout 2.96 to about 3.08 and lanthanum mole fractions ranging from about0.92 to about 1.04. Thus, the exemplary embodiment in which the yttriummole fraction is three and the lanthanum mole fraction is one isprovided for purposes of illustration and not intended to limitembodiments of the present invention.

Another object of some embodiments of the present invention is relatedto the formation of a particular phase that is stabilized within thecompositional range of compounds described herein. The generalstoichiometry of Y₃LaAl₁₂B₁₆O₄₈ consistently forms under a limited rangeof starting compositions. Three of the four starting materials (i.e.,yttrium, lanthanum, and boron oxides) are used in stoichiometric excessto act as a solvent in addition to being nutrients for crystal formationof the principal compound. Table 2 lists several starting materialcompositions that yield the new crystalline phase. The values for thestarting materials listed in Table 2 are not intended to be exhaustive,but to illustrate starting compositions that may be used to formcrystals having the desired chemical composition. Other startingmaterial compositions are therefore included within the scope ofembodiments of the present invention.

TABLE 2 Yttrium:lanthanum:aluminum:borate molar composition and crystalratios and resulting crystal formulae Starting Metal Crystalline OxideComposition Composition Measured Data Y:La:Al:B Y:La:Al:B CrystalFormula 4:8:12:44 3:1:12:16 Y_(3.00)La_(1.00)Al_(12.00)B₁₆O₄₈ 4:9:12:483:1:12:16 Y_(3.04)La_(0.96)Al_(12.00)B₁₆O₄₈ 4:6:12:40 3:1:12:16Y_(3.08)La_(0.96)Al_(11.96)B₁₆O₄₈

In addition to the starting metal oxide compositions listed in Table 2,other starting compositions are included within the scope of embodimentsof the present invention. For example, the ratios 3:8:12:44, 4:6:12:38,4:7:12:41, 4:12:12:56, 4:10:12:50, are proportions suitable to producecrystals that satisfy the compositional invention. Due to the range ofexcess starting concentrations of boron and lanthanum to act as amixture's solvent, the molar ratio of boron to lanthanum can range from4:1 to 10:1. In some embodiments, the constituent components arecharacterized by a predetermined amount of nutrients, i.e., the startingmaterial sources of elements that contribute to the stoichiometriccrystalline end product, and a predetermined amount of solvents, i.e.,other starting materials that do not contribute to the stoichiometriccrystalline end product but may constitute excess amounts of the verysame nutrient starting materials. The mole ratio of the predeterminedamount of solvents to the predetermined amount of nutrients ranges fromabout 1:1 to about 1:5. In a particular embodiment, the ratio oflanthanum to yttrium is more than 1.5:1, for example, 2:1 or 3:1.

The crystal structures provided by embodiments of the present inventionare derived from a non-congruent melt of nutrient oxides, so solvent(s)are needed to reduce the melt temperature below the peritecticdecomposition temperature of about 1575 K. In this method, thestoichiometric excess of yttrium, lanthanum, and boron oxides in thestarting materials composition serve as a solvent for the principalcompound formed during single crystal growth. As shown in Table 2, theextracted crystal composition nominally remains the same as determinedby elemental analyses, regardless of the illustrated variations in thestarting material proportions. Thus, the crystallized materialrepresents a thermodynamically-stabilized new phase, rather than merelybeing a composition along a solid-solution continuum. As such,variations in the starting materials (e.g., starting Y:La:Al:Bcompositions of either 4:8:12:44 or 4:9:12:48) will result in acrystallized material having the crystalline composition of 3:1:12:16.The remaining materials left behind in the crucible after the singlecrystal growth process represent a mixture of excess solvating yttrium,lanthanum, and boron oxides along with uncrystallized principalmaterial. The inventor has appreciated that although a range of molefractions for the elements of the composition are theoreticallypossible, the actual ranges that result in thermodynamically-stabilizedphases are limited. Additionally, in order to provide a NLO materialthat is suitable for optical applications (for example, at UVwavelengths less than 360 nm), the crystallographic structure of thestable phase is only one of the material properties of interest. Othermaterial properties including resultant refractive indices for favorablephase matching at operating wavelengths, transmittance at operatingwavelengths, the nonlinear drive derived from the structuralnon-centrosymmetric arrangement, and the like are provided concurrentlywith the stability of the phase in NLO crystals provided by embodimentsof the present invention. Thus, large theoretical ranges are merelythat, theoretical ranges that infrequently provide actual crystalsuseful for nonlinear optics applications.

Embodiments of the present invention provide a predetermined amount oflanthanum in order to provide a solvent for the crystal melt, howeverother solvent modifiers may be utilized. Thus, some of the methods andprocesses described herein utilize an excess of lanthanum and/or boronmaterials to provide solvent functionality typically provided by K₂MoO₄and K₂Mo₃O₁₀ or other solvents. By using materials present in the finalcrystalline composition as a solvent, the incorporation of UV absorbingelements are reduced or eliminated, providing for high transmissionproperties in the UV range of the spectrum. In addition, common solventsthat are not known to impede UV transmittance may be used for hightemperature crystal growth of the principal compound. For example,lithium borates may be utilized as secondary solvent modifiers to affectmelt acidity and thereby modify the mixture's solvation of nutrientconstituents, e.g. lithium tetraborate acts as an acidic solvent flux,and lithium metaborate is an accustomed basic solvent flux. Theviscosity of the charge mixture can also be modified by the addition ofcommon alkali metal halides, e.g. lithium, sodium, or potassiumfluorides. Again, fluxing agents are selected so as to avoid moietiesthat impede UV transmittance and to preclude general incorporation intothe crystal structure.

The resulting principal compound was determined to be isostructural tothe mineral CaMg₃C₄O₁₂, huntite. Added to the family of huntite borateanalogs, yttrium lanthanum aluminum borate forms in the trigonal system,rhombohedral class in the space group R32. Table 3 lists representativecrystallographic data and other physical properties for Y₃LaAl₁₂B₁₆O₄₈.

TABLE 3 Physical properties of Y₃LaAl₁₂B₁₆O₄₈ crystal Y₃LaAl₁₂B₁₆O₄₈Class Rhombohedral Space Group R32 a 588.5 pm α 104.3° Crystal density3.76 g/cm³ Color colorless Optical axes uniaxial Hardness 7 MohsMorphology Trapezohedral Cleavage (100) Hygroscopicity none

According to an embodiment of the present invention, the NLO materialsdescribed herein are manufactured by a method that eliminates orsignificantly reduces contaminants that prohibit device use in the UVspectrum. More specifically, some embodiments of the present inventionsubstantially exclude elements, such as 3d-5d transition metals and 4flanthanides other than Y, La, and Lu, from being present in the opticaldevice. The absence of these elements enables device operation forapplications such as lasers, frequency converters and other opticaldevices at wavelengths in the UV below 360 nm.

FIG. 2 is a simplified image of an optical compound according to anembodiment of the present invention. This diagram is merely an example,which should not unduly limit the scope of the claims. One of ordinaryskill in the art would recognize many variations, alternatives, andmodifications. The optical compound includes Y_(i)La_(j)Al_(k)B₁₆O₄₈,where 2.8≦i≦3.2, 0.8≦j≦1.2, i and j sum to about four, and k is about12, made by the method 100 as discussed above. The synthesis starts withyttrium oxide (Y₂O₃), lanthanum oxide (La₂O₃), aluminum oxide (Al₂O₃),and boron oxide (B₂O₃), all reagents having purities greater than 99.9%.As shown in FIG. 2, the 20×15×10 mm crystal is sufficiently large andpossesses optical transparency that enables it to function as a laserlight modification device.

FIG. 3 is a simplified diagram showing transmission characteristics foran optical compound according to an embodiment of the present invention.This diagram is merely an example, which should not unduly limit thescope of the claims. One of ordinary skill in the art would recognizemany variations, alternatives, and modifications. The optical compoundincludes Y_(i)La_(j)Al_(k)B₁₆O₄₈, where 2.8≦i≦3.2, 0.8≦j≦1.2, i and jsum to about four, and k is about 12, made by the method 100 asdiscussed above. The synthesis starts with yttrium oxide (Y₂O₃),lanthanum oxide (La₂O₃), aluminum oxide (Al₂O₃), and boron oxide (B₂O₃).As shown in FIG. 3, a curve 300 shows the transmission percentage as afunction of wavelength. The transmission percentage does not vary due toabsorption features from 360 nm to about 175 nm. It should be noted thatthe transmission characteristics illustrated in FIG. 3 do not accountfor Fresnel losses at interfaces. Thus, the actual percent of powertransmitted through the optical compound is actually higher thanillustrated by the data shown in FIG. 3. The inventors believe that thetransmission percentage can be over 75%, over 80%, over 85%, over 90% orover 95% at given wavelengths.

FIG. 4A is a simplified diagram showing frequency conversion by anoptical compound according to an embodiment of the present invention.This diagram is merely an example, which should not unduly limit thescope of the claims. One of ordinary skill in the art would recognizemany variations, alternatives, and modifications. The optical compoundincludes Y_(i)La_(j)Al_(k)B₁₆O₄₈, where 2.8≦i≦3.2, 0.8≦j≦1.2, i and jsum to about four, and k is about 12, made by the method 100 asdiscussed above. The synthesis starts with yttrium oxide (Y₂O₃),lanthanum oxide (La₂O₃), aluminum oxide (Al₂O₃), and boron oxide (B₂O₃).For example, the optical compound is the crystal as shown in FIG. 2.During the experiment and by way of example, laser light with awavelength of about 532 nm was delivered to a Y₃LaAl₁₂B₁₆O₄₈ crystalgreater than 1 mm³ in size. In response, the crystal output a light beamreceived by an imaging scintillator card, which was sensitive toultraviolet radiation. As shown in FIG. 4A, an image was taken using acamera that was made blind to 532 nm with a filter for the photograph.

For the benefit of a photographed image, a scintillator card is used tovisibly detect the presence of the 266 nm radiation and a bluefluorescence spot image was observed. Hence ultraviolet light wasgenerated by the Y₃LaAl₁₂B₁₆O₄₈ crystal through a SHG process and wasdetected by the imaging scintillator card. In another demonstration, abandpass mirror specific for 266 nm light transmission was placedbetween the Y₃LaAl₁₂B₁₆O₄₈ crystal and the imaging scintillator card.Blue fluorescence, which is caused by UV radiation similar to that inFIG. 4A, was also observed, and FIG. 4B is the output spectral profileof the converted 266 nm light. Hence, deep ultraviolet light at 266 nmwas generated by the Y₃LaAl₁₂B₁₆O₄₈ crystal.

As discussed above, and further emphasized here, the method can be usedto make various types of optical compounds. According to one embodimentof the present invention, a compound for nonlinear optics for use atwavelengths of 175-360 nm is made by the method 100. The compoundincludes a material for nonlinear optics comprising Y₃LaAl₁₂B₁₆O₄₈. Thecompound is free from bearing UV-blocking impurities of at least 1000parts per million. According to yet another embodiment of the presentinvention, a compound for nonlinear optics for use at wavelengths of175-360 nm is made by the method 100. The compound may comprise amaterial for nonlinear optics includes R_(i)La_(j)Al_(k)B₁₆O₄₈, where2.0≦i≦3.6, 0.4≦j≦2.0, i and j sum to about four, k is about 12, and R isselected from an elemental group consisting of Y and Lu. The compoundmay also comprise a material for nonlinear optics includesY_(i)La_(j)Al_(k)B₁₆O₄₈, where 2.8≦i≦3.2, 0.8≦j≦1.2, i and j sum toabout four, and k is about 12. The compound is free from bearingUV-blocking impurities of at least 1000 parts per million.

As discussed above, according to certain embodiments, each of varioustypes of optical compounds made by the method 100 is free from bearingUV-blocking impurities of at least 1000 parts per million. For example,the compound is free from bearing UV-blocking impurities of at least 500parts per million. In another example, the compound is free from bearingUV-blocking impurities of at least 100 parts per million. In yet anotherexample, the compound is free from bearing UV-blocking impurities of atleast 10 parts per million. In yet another example, the compound is freefrom bearing UV-blocking impurities of at least 1 part per million. Inyet another example, the compound is substantially free from bearingUV-blocking impurities. According to some embodiments of the presentinvention, each of various types of optical compounds made by the method100 each is free from any impurity of at least 1000 parts per millionthat can prevent the compound from being used for nonlinear optics at360 nm and below. For example, the compound is free from any suchimpurity of at least 500 parts per million. In another example, thecompound is free from any such impurity of at least 100 parts permillion. In yet another example, the compound is free from any suchimpurity of at least 10 parts per million. In yet another example, thecompound is free from any such impurity of at least 1 part per million.In yet another example, the compound is substantially free from any suchimpurity.

As discussed above, according to certain embodiments, each of varioustypes of optical compounds made by the method 100 has a volume greaterthan about 0.01 mm³. In another embodiment, the volume of the NLOmaterials may be greater than about 0.1 mm³. It will be appreciated thatdepending on the application, the crystal volume may be limited in sizeas appropriate to the particular application, for example a volume ofless than about 1,000 cm³. For example, the compound has a volumegreater than about 0.1 mm³ or about 1 mm³. In another example, thecompound has a volume greater than about 10 mm³.

According to some embodiments, various types of optical compounds madeby the method 100 can be used for nonlinear optics at 360 nm and below.For example, the use is associated with a wavelength ranging from about360 nm to 175 nm. In yet another example, the use is associated with adevice that generates optical radiation below 360 nm. In yet anotherexample, the device comprises an NLO system, the compound associatedwith a laser system, and/or the compound associated with a light source.

According to certain embodiments, the method 100 can be used to make acompound for nonlinear optics for use at 360 nm and below. For example,the compound is associated with the trigonal crystal class and may beused for applications below 360 nm. In another example, the compound isassociated with space group R32 and may be used for applications below360 nm.

According to yet another embodiment of the present invention, a methodfor making a compound for nonlinear optics for use at wavelengths of175-360 nm includes providing a plurality of materials. The plurality ofmaterials includes a lanthanum bearing compound, and the lanthanumbearing compound is capable of being decomposed into at least lanthanumoxide upon heating. Additionally, the method includes mixing theplurality of materials to form a mixture based on at least informationassociated with a predetermined proportion, starting a crystallizationprocess in the mixture to form a crystal, and removing the crystal fromthe mixture, the crystal including lanthanum. For example, the pluralityof materials comprises lanthanum oxide. In another example, theplurality of material further comprises boron oxide. In yet anotherexample, the method further includes placing the mixture into a furnace.In yet another example, the method further includes heating the mixtureto a first predetermined temperature, and cooling the mixture to asecond predetermined temperature. In yet another example, the starting acrystallization process comprises inserting a crystalline seed to a meltsurface. In yet another example, the crystal includesY_(i)La_(j)Al_(k)B₁₆O₄₈, where 2.8≦i≦3.2, 0.8≦j≦1.2, i and j sum toabout four, and k is about 12. In yet another example, the method isimplemented according to the method 100.

According to yet another embodiment of the present invention, a methodfor making a compound for nonlinear optics for use at wavelengths of175-360 nm includes providing a plurality of materials. The plurality ofmaterials includes an yttrium bearing compound, and the yttrium bearingcompound is capable of being decomposed into at least yttrium oxide uponheating. Additionally, the method includes mixing the plurality ofmaterials to form a mixture based on at least information associatedwith a predetermined proportion, starting a crystallization process inthe mixture to form a crystal, and removing the crystal from themixture, the crystal including yttrium. For example, the plurality ofmaterials includes yttrium oxide. In another example, the plurality ofmaterial further includes boron oxide. In yet another example, themethod further includes placing the mixture into a furnace. In yetanother example, the method further includes heating the mixture to afirst predetermined temperature, and cooling the mixture to a secondpredetermined temperature. In yet another example, the starting acrystallization process comprises inserting a crystalline seed to a meltsurface. In yet another example, the crystal includesY_(i)La_(j)Al_(k)B₁₆O₄₈, where 2.8≦i≦3.2, 0.8≦j≦1.2, i and j sum toabout four, and k is about 12. In yet another example, the method isimplemented according to the method 100.

It is understood the examples and embodiments described herein are forillustrative purposes only and that various modifications or changes inlight thereof will be suggested to persons skilled in the art and are tobe included within the spirit and purview of this application and scopeof the appended claims.

1. A method of growing one or more nonlinear crystals of a composition,the method comprising: providing a set of constituent components of thecomposition including an yttrium source, a lanthanum source, a boronsource, and an aluminum source; mixing the set of constituent componentsof the composition to form a component mixture; heating the componentmixture to a predetermined temperature, thereby forming a resultantmelt; cooling the resultant melt; and forming the one or more nonlinearcrystals of the composition as a precipitate from the resultant melt,wherein the one or more nonlinear crystals have a chemical formula ofY_(i)La_(j)Al_(k)B₁₆O₄₈, where 2.0≦i≦3.6, 0.4≦j≦2.0, i and j sum toabout four, and k is about
 12. 2. The method of claim 1 wherein theyttrium source comprises yttrium oxide, the lanthanum source compriseslanthanum oxide, and the aluminum source comprises aluminum oxide. 3.The method of claim 3 wherein the boron source comprises at least one ofboron oxide or boric acid.
 4. The method of claim 3 wherein the one ormore nonlinear crystals are characterized by an optical transmittance ofgreater than 0.7 at 250 nm.
 5. The method of claim 4 wherein the opticaltransmittance is greater than 0.7 at 200 nm.
 6. The method of claim 1wherein a concentration of at least one or more of elements 22-30,40-48, and 72-80 in the one or more nonlinear crystals is less than1,000 parts per million.
 7. The method of claim 1 wherein aconcentration of molybdenum in the one or more nonlinear crystals isless than 50 parts per million.
 8. The method of claim 1 wherein aconcentration of at least one or more of elements 58-70 in the one ormore nonlinear crystals is less than 1,000 parts per million.
 9. Themethod of claim 1 wherein cooling the resultant melt is performed at atemperature rate of less than 20° K/hour.
 10. The method of claim 1wherein the one or more nonlinear crystals are characterized by a volumebetween about 1.0 mm³ and about 10 cm³.